LAUSR

Organic aerogels are an intriguing class of highly porous and ultralight materials which have found widespread applications in thermal insulation, energy storage, and chemical absorption. These fully cross‐linked polymeric networks, however, pose environmental concerns as they are typically made from fossil‐based feedstock and the recycling back to their original monomers is virtually impossible. In addition, organic aerogels suffer from low thermal stability and potential fire hazard. To overcome these obstacles and create next‐generation organic aerogels, a set of polyimine aerogels containing reversible chemical bonds which can selectively be cleaved on demand is prepared. As precursors, different primary amines and cyclophosphazene derivatives made from bio‐based reagents (vanillin and 4‐hydroxybenzaldehyde) to elevate the thermal stability and reduce the environmental impact are used. The resulting polyimine aerogels exhibit low shrinkage, high porosity, large surface area, as well as pronounced thermal stability and flame resistance. More importantly, the aerogels show excellent recyclability under acidic conditions with high monomer recovery yields and purities. This approach allows for preparation of fresh aerogels from the retrieved building blocks, thus demonstrating efficient closed‐loop recycling. These high‐performance, recyclable, and bio‐based polyimine aerogels pave the way for advanced and sustainable superinsulating materials.